Fabric care method

ABSTRACT

The present invention provides a process for inhibiting the re-absorption of migrating dyes in the wash liquor, comprising introducing into a wash liquor containing a peroxide-containing detergent, from 0.5 to 150, preferably from 1.5 to 75, especially from 7.5 to 40 mg, per liter of wash liquor, of one or more compounds having the formula:  
                 
 
     in which n is 1, 2 or 3; A is an anion;  
     Y is —(CH 2 ) m  in which m is an integer ranging from 1 to 8; —(CH 2 ) p —CH(R 1 )—in which p is an integer ranging from 1 to 7 and R 1  is linear or branched C 1 -C 4 -alkyl, preferably methyl; —CX═CX— in which X is cyano, linear or branched C 1 -C 8 -alkyl or di(linear or branched C 1 -C 8 -alkyl)-amino;  
     —(CH 2 ) q —NR 1 —(CH 2 ) q — in which R 1  has its previous significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene residue having the formula:  
                 
 
     R is cyano; halogen; hydroxy; OR 1  in which R 1  has its previous significance; CO 2 R 2  in which R 2  is hydrogen or linear or branched C 1 -C 4 -alkyl; nitro; linear or branched C 1 -C 8 -alkyl;  
     di-(C 4 -C 12 alkyl)amino; NR 3 R 4  in which R 3  and R 4  are the same or different and each is linear or branched C 1 -C 12 -alkyl; or —N⊕R 1 R 3 R 4  in which R 1 , R 3  and R 4  have their previous significance.

[0001] The present invention relates to a process for inhibiting there-absorption of migrating dyes in the wash liquor.

[0002] It is well known that various metal compounds, e.g. manganesecomplexes, are useful in detergents as catalysts for oxidation withperoxygen compounds such as perborate or peroxides. It is also knownthat certain other manganese complexes cause enhanced bleaching effectson dirt or dyes in the wash bath. Moreover, these manganese complexes donot exhaust at all on to cotton, polyamide or polyester fibers so thatthe complexes cannot lead to fiber discoloration problems.

[0003] One problem associated with the evaluation of a compound as acandidate for use in a process for inhibiting the re-absorption ofmigrating dyes in the wash liquor, is the lack of a sufficientlyreliable and comprehensive screening technique. Such a technique has nowbeen developed and used to quantify the dye transfer inhibitionperformance of potential substances. This screening procedure comprisesa variety of tests which makes it possible to determine theusefulness/damage balance of any candidates on a quantitative basis. Aproduct is characterised in terms of its specific effectivity, scope ofuse, compatibility with the most important system components, oxygendemand and its fiber- and dyestuff degradation potential. Moreover, theprecision of the data is such that structure/effect relationships can bedeveloped. The application of the new evaluation technique to manganesecomplexes has resulted in the identification of further manganesecomplexes which exhibit excellent performance as dye transferinhibitors, which are of relatively low molecular weight and theeffectiveness of which is substantial even at low levels of addition.

[0004] Accordingly, the present invention provides a process forinhibiting the re-absorption of migrating dyes in the wash liquor,comprising introducing into a wash liquor containing aperoxide-containing detergent, from 0.5 to 150, preferably from 1.5 to75, especially from 7.5 to 40 mg, per liter of wash liquor, of one ormore compounds having the formula:

[0005] in which n is 1, 2 or 3;

[0006] A is an anion;

[0007] R₁ is hydrogen or C₁-C₄-alkyl,

[0008] Y is linear or branched alkylene of the formula —[C(R₁)₂]_(m) inwhich m is an integer ranging from 1 to 8 and each R₁ independently fromthe other has its previous significance; —CX═CX— in which X is cyano,linear or branched C₁-C₈-alkyl or di(linear or branchedC₁-C₈-alkyl-amino;

[0009] —(CH₂)_(q)—NR₁(CH₂)_(q)— in which R₁ has its previoussignificance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenyleneresidue having the formula:

[0010] in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M ishydrogen, an alkali metal atom, ammonium or a cation formed from anamine,

[0011] R and R′ are each independently from the other cyano; halogen;hydroxy; OR₁ or COOR₁ in which R₁ has its previous significance; nitro;linear or branched partially or completely fluorinated C₁-C₈-alkyl;NR₃R₄ in which R₃ and R₄ are the same or different and each is hydrogenor linear or branched C₁-C₁₂-alkyl; -N⊕R₁R₃R₄ in which R₁, R₃ and R₄have their previous significance or linear or branched C₁-C₈-alkylene-R₂in which R₂ is OR₁, COOR₁ or NR₃R₄,

[0012] R₅ and R₆ are each independently from the other hydrogen; linearor branched C₁-C₄-alkyl; unsubstituted aryl or aryl which is substitutedby cyano, halogen, OR₁ or COOR₁, nitro, linear or branched C₁-C₈-alkyl,NR₃R₄ in which R₃ and R₄ are the same or different and each is hydrogenor linear or branched C₁-C₁₂-alkyl; -N⊕R₁R₃R₄ in which R₁, R₃ and R₄have their previous significance or linear or branched C₁-C₈-alkylene-R₂in which R₂ is OR₁, COOR₁ or NR₃R₄,

[0013] with the proviso that each n is 1, if R and R′ are bothC₁-C₄-alkyl.

[0014] When Y is a 1,2-cyclohexylene residue, this residue may be in anyof its cis/trans stereoisomeric forms.

[0015] Y is preferably —[C(R₈)₂]₂ wherein R₈ is hydrogen or methyl,—CX═CX— in which X is cyano, —(CH₂)_(q)—NR₈—(CH₂)_(q)— in which R₈ hasits previous significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexyleneor phenylene residue having the formula:

[0016] Preferred halogen atoms R or R′ are chlorine, bromine andfluorine atoms.

[0017] When n is 1, preferably the group R or R′ respectively is in the4-position of the respective benzene ring, with the exceptions that whenR or R′ is nitro or CO₂R₂, the group R or R′ is preferably in the5-position of the respective benzene ring. When n is 2, preferably thegroups R or R′ are in the 4,6-positions of the respective benzene ring,with the exceptions that when R or R′ is nitro or CO₂R₂ the groups R orR′ are preferably in the 3,5-positions of the respective benzene ring.

[0018] When R or R′ is the group di-(C₁-C₁₂alkyl)amino, the alkyl moietymay be a straight- or branched chain alkyl moiety, and it preferablycontains from 1 to 8, more preferably from 1 to 4 and, especially, 1 or2 carbon atoms.

[0019] Preferred groups R and R′ are dimethylamino, diethylamino,hydroxy, methoxy, ethoxy, chloro or nitro.

[0020] Anions A include halide, especially chloride, perchlorate,sulphate, nitrate, hydroxide, BF₄ ⁻, PF₆ ⁻, carboxylate, especiallyacetate, triflate or tosylate.

[0021] Some of the compounds of formula (1) and the ligands from whichthey are derived are known compounds. For example, in U.S. Pat. No.5,281,578 there is described the preparation ofN,N-bis(4-dimethylaminosalicylidene)diiminoethylene; in EP-A-0 693 550there is disclosed the production of the manganese complex ofN,N-bis(4-diethylaminosalicylidene)diiminoethylene; and in Bernadoet.al., Inorg. Chem. 35 (2) 387 (1996), there is disclosed theproduction of N,N-bis(4-diethylaminosalicylidene)diiminocyclohexylene aswell as the production of the manganese complexN,N-bis(4-diethylaminosalicylidenediiminocyclohexylene. New compounds offormula (1) and new ligands from which they are derived form furtheraspects of the present invention.

[0022] Moreover, the use, as dye transfer inhibitors, of those compoundsof formula (1) in which A is an anion and a) Y is —CH₂CH₂— each R isdi-(C₁-C₂alkyl)amino; or b) Y is cyclohexylene and each R isdi-(C₁-C₂alkyl)amino has been broadly indicated, but not specificallydescribed, in GB-A-2,296,015. On the other hand, the use, as dyetransfer inhibitors, of those compounds of formula (1) in which A is ananion, Y is —CH₂CH₂— and each R is hydroxy, is believed to be completelynew.

[0023] Of particular interest for use in in the method of the presentinvention are those compounds of formulae:

[0024] The present invention also provides a detergent compositioncomprising:

[0025] i) 5-90%,preferably 5-70% of A) an anionic surfactant and/or B) anonionic surfactant;

[0026] ii) 5-70%, preferably 5-50%, especially 5-40% of C) a builder;

[0027] iii) 0.1-30%, preferably 1-12% of D) a peroxide; and

[0028] iv) 0.005-2%, preferably 0.02-1%, especially 0.1-0.5% of E) acompound of formula (1) or (2) as defined above, each by weight, basedon the total weight of the detergent.

[0029] The detergent may be formulated as a solid; or as a non-aqueousliquid detergent, containing not more than 5, preferably 0-1 wt.% ofwater, and based on a suspension of a builder in a non-ionic surfactant,as described, e.g., in GB-A-2158454.

[0030] Preferably, the detergent is in powder or granulate form.

[0031] Such powder or granulate forms may be produced by firstly forminga base powder by spray-drying an aqueous slurry containing all the saidcomponents, apart from the components D) and E); then adding thecomponents D) and E) by dry-blending them into the base powder. In afurther process, the component E) may be added to an aqueous slurrycontaining components A), B) and C), followed by spray-drying the slurryprior to dry-blending component D) into the mixture. In a still furtherprocess, component B) is not present, or is only partly present in anaqueous slurry containing components A) and C); component E) isincorporated into component B), which is then added to the spray-driedbase powder; and finally component D) is dry-blended into the mixture.

[0032] The anionic surfactant component A) may be, e.g., a sulphate,sulphonate or carboxylate surfactant, or a mixture of these. Preferredsulphates are alkyl sulphates having 12-22 carbon atoms in the alkylradical, optionally in combination with alkyl ethoxy sulphates having10-20 carbon atoms in the alkyl radical.

[0033] Preferred sulphonates include alkyl benzene sulphonates having9-15 carbon atoms in the alkyl radical.

[0034] In each case, the cation is preferably an alkali metal,especially sodium.

[0035] Preferred carboxylates are alkali metal sarcosinates of formulaR—CO—N(R¹)—CH₂COOM¹ in which R is alkyl or alkenyl having 9-17 carbonatoms in the alkyl or alkenyl radical, R′ is hydrogen or C₁-C₄ alkyl andM¹ is alkali metal.

[0036] The nonionic surfactant component B) may be, e.g., a condensateof ethylene oxide with a C₉-C₁₅ primary alcohol having 3-8 moles ofethylene oxide per mole.

[0037] The builder component C) may be an alkali metal phosphate,especially a tripolyphosphate; a carbonate or bicarbonate, especiallythe sodium salts thereof; a silicate; an aluminosilicate; apolycarboxylate; a polycarboxylic acid; an organic phosphonate; or anaminoalkylene poly (alkylene phosphonate); or a mixture of these.

[0038] Preferred silicates are crystalline layered sodium silicates ofthe formula NaHSi_(m)O_(2m+1),pH₂O or Na₂Si_(m)O_(2m+1),pH₂O in which mis a number from 1.9 to 4 and p is 0 to 20.

[0039] Preferred aluminosilicates are the commercially-availablesynthetic materials designated as Zeolites A, B, X, and HS, or mixturesof these. Zeolite A is preferred.

[0040] Preferred polycarboxylates include hydroxypolycarboxylates, inparticular citrates, polyacrylates and their copolymers with maleicanhydride.

[0041] Preferred polycarboxylic acids include nitrilotriacetic acid andethylene diamine tetra-acetic acid, ethylenediaminedisuccinate inracemic form as well as the enantiomeric S,S-form

[0042] Preferred organic phosphonates or aminoalkylene poly (alkylenephosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilotrimethylene phosphonates, ethylene diamine tetra methylene phosphonatesand diethylene triamine penta methylene phosphonates.

[0043] The peroxide component D) may be any organic or inorganicperoxide compound, described in the literature or available on themarket, which bleaches textiles at conventional washing temperatures,e.g. temperatures in the range of from 30° C. to 90° C. In particular,the organic peroxides are, for example, monoperoxides or polyperoxideshaving alkyl chains of at least 3, preferably 6 to 20, carbon atoms; inparticular diperoxydicarboxylates having 6 to 12 C atoms, such asdiperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/ordiperoxydodecanedioates, especially their corresponding free acids, areof interest. It is preferred, however, to employ very active inorganicperoxides, such as persulphate, perborate and/or percarbonate. It is, ofcourse, also possible to employ mixtures of organic and/or inorganicperoxides. Peroxides can have different crystalline forms and/ordifferent degrees of hydration. They may be used in admixture with otherorganic or inorganic salts, thereby improving their stability tostorage.

[0044] The addition of the peroxides to the detergent is effected, inparticular, by mixing the components, for example by means ofscrew-metering systems and/or fluidized bed mixers.

[0045] The detergents may contain, in addition to the combinationaccording to the invention, one or more of fluorescent whitening agents,such as a bis-triazinylamino-stilbene-disulphonic acid, abis-triazolyl-stilbene-disulphonic acid, a bis-styryl-biphenyl, abis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, abis-benzimidazolyl derivative, a coumarine derivative or a pyrazolinederivative; soil suspending agents, for example sodiumcarboxymethylcellulose; salts for adjusting the pH, for example alkalior alkaline earth metal silicates; foam regulators, for example soap;salts for adjusting the spray drying and granulating properties, forexample sodium sulphate; perfumes; and also, if appropriate, antistaticand softening agents; such as smectite clays; enzymes, such as amylases;photobleaching agents; pigments; and/or shading agents. Theseconstituents should, of course, be stable to the bleaching systememployed.

[0046] A particularly preferred detergent co-additive is a polymer knownto be useful in preventing the transfer of labile dyes between fabricsduring the washing cycle. Preferred examples of such polymers arepolyvinyl pyrrolidones, optionally modified by the inclusion of ananionic or cationic substituent, especially those having a molecularweight in the range from 5000 to 60,000, in particular from 10,00 to50,000. Preferably, such polymer is used in an amount ranging from 0.05to 5%, preferably 0.2-1.7% by weight, based on the weight of thedetergent.

[0047] The detergents may additionally contain so-calledperborate-activators, e.g. TAGU or, preferably TAED. This is preferablyused in an amount of 0,05 through 5 % by weight, especially 0,2 through1,7 % by weight, relative to the total weight of the detergent.

[0048] The manganese complexes of formula (2) are new compounds and someof the manganese complexes of formula (1) are new too.

[0049] The invention consequently also relates to manganese complexes offormula (3)

[0050] in which n is, 2 or 3; p1 A is an anion;

[0051] R and R′ are each independently from the other cyano; halogen;hydroxy; OR₁ or COOR₁ in which R₁ has its previous significance; nitro;linear or branched partially or completely fluorinated C₁-C₈-alkyl;NR₃R₄ in which R₃ and R₄ are the same or different and each is hydrogenor linear or branched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄have their previous significance or linear or branched C₁-C₈-alkylene-R₂in which R₂ is OR₁, COOR₁ or NR₃R₄,

[0052] R₁ is hydrogen or C₁-C₄-alkyl,

[0053] Y₁ is —CX═CX— in which X is cyano, —(CH₂)_(q)—NR₁—(CH₂)_(q)— inwhich R₁ has its previous significance and q is 1, 2, 3 or 4; linear orbranched alkylene of the formula —[C(R₁)₂]_(m) in which m is an integerranging from 1 to 8 and each R₁ independently from the other has itsprevious significance, with the proviso that at least one R₁ isC₁-C₄-alkyl; or a 1,2-cyclohexylene or phenylene residue having theformula:

[0054] in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M ishydrogen, an alkali metal atom, ammonium or a cation formed from anamine, with the proviso that each n is 1 if R and R′ are bothC₁-C₄-alkyl and Y₁ is an unsubstituted 1,2-cyclohexylene residue,

[0055] Y is linear or branched alkylene of the formula —[C(R₁)₂]_(m) inwhich m is an integer ranging from 1 to 8 and each R₁ independently fromthe other has its previous significance; —CX═CX— in which X is cyano,linear or branched C₁-C₈-alkyl or di(linear or branchedC₁-C₈-alkyl)-amino;

[0056] —(CH₂)_(q)—NR₁—(CH₂)_(q) — in which R₁ has its previoussignificance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenyleneresidue having the formula:

[0057] in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M ishydrogen, an alkali metal atom, ammonium or a cation formed from anamine,

[0058] R₅ and R₆ are each independently from the other hydrogen; linearor branched C₁-C₄-alkyl; unsubstituted aryl or aryl which is substitutedby cyano, halogen, OR₁ or COOR₁, nitro, linear or branched C₁-C₈-alkyl,NR₃R₄ in which R₃ and R₄ are the same or different and each is hydrogenor linear or branched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄have their previous significance or linear or branched C₁-C₈-alkylene-R₂in which R₂ is OR₁, COOR₁ or NR₃R₄.

[0059] The ligands of formulae (4) or (5) which are contained in themanganese complexes are new themselves and these ligands are also partof the instant invention. The invention consequently also relates tocompounds of the formula (4)

[0060] in which n is 1, 2 or 3;

[0061] R and R′ are each independently from the other cyano; halogen;hydroxy; OR₁ or COOR₁ in which R₁ has its previous significance; nitro;linear or branched partially or completely fluorinated C₁-C₈-alkyl;NR₃R₄ in which R₃ and R₄ are the same or different and each is hydrogenor linear or branched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄have their previous significance or linear or branched C₁-C₈-alkylene-R₂in which R₂ is OR₁, COOR₁ or NR₃R₄,

[0062] R₁ is hydrogen or C₁-C₄-alkyl,

[0063] Y₁ is —CX═CX— in which X is cyano, —(CH₂)_(q)—NR₁—(CH₂)_(q)— inwhich R₁ has its previous significance and q is 1, 2, 3 or 4; linear orbranched alkylene of the formula —[C(R₁)₂]_(m) in which m is an integerranging from 1 to 8 and each R₁ independently from the other has itsprevious significance, with the proviso that at least one R₁ isC₁-C₄-alkyl; or a 1,2-cyclohexylene or phenylene residue having theformula:

[0064] in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M ishydrogen, an alkali metal atom, ammonium or a cation formed from anamine, with the proviso that each n is 1 if R and R′ are bothC₁-C₄-alkyl and Y₁ is an unsubstituted 1,2-cyclohexylene residue,

[0065] Y is linear or branched alkylene of the formula —[C(R₁)₂]_(m) inwhich m is an integer ranging from 1 to 8 and each R₁ independently fromthe other has its previous significance; —CX═CX— in which X is cyano,linear or branched C₁-C₈-alkyl or di(linear or branchedC₁-C₈-alkyl)-amino;

[0066] —(CH₂)_(q)—NR₁—(CH₂)_(q)— in which R₁ has its previoussignificance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenyleneresidue having the formula:

[0067] in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M ishydrogen, an alkali metal atom, ammonium or a cation formed from anamine,

[0068] R₅ and R₆ are each independently from the other hydrogen; linearor branched C₁-C₄-alkyl; unsubstituted aryl or aryl which is substitutedby cyano, halogen, OR₁ or COOR₁, nitro, linear or branched C₁-C₈-alkyl,NR₃R₄ in which R₃ and R₄ are the same or different and each is hydrogenor linear or branched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄have their previous significance or linear or branched C₁-C₈-alkylene-R₂in which R₂ is OR₁, COOR₁ or NR₃R₄.

[0069] Preferred compounds of formula (4) are the following:

[0070] Preferred compounds of formula (5) are

[0071] The following Examples serve to illustrate the invention; partsand percentages are by weight, unless otherwise stated.

Preparation of the New Ligands Ligand 2a

[0072] a) Preparation of the corresponding aldehyde

[0073] Firstly, the starting compoundN,N-dibutyl-4-amino-2-hydroxy-benzaldehyde had to be prepared byVilsmeyer formylation of N,N-dibutyl-3-amino-phenol. The Vilsmeyerreagent was prepared by slow addition of 4.7 ml (0.0497 mol) ofphosphorus oxychloride to 15 ml (0.189 mol) of N,N-dimethyl formamidewith stirring for 15 minutes at room temperature. Stirring was continuedfor 30 more minutes before this Vilsmeyer reagent was used. 11 g (0.497mol) N,N-dibutyl-3-amino-phenol, prepared by alkylation of 3-aminophenolafter the procedure described in EP 0356173 was dissolved in 13 mlN,N-dimethyl formamide. This solution was added dropwise at roomtemperature to the Vilsmeyer reagent described above. The solution wasstirred for 3 h, heated to 50° C. for 10 minutes. The solution wascooled to room temperature and stirred for another 2 h. Then, thereaction mixture was poured onto 70 g ice and stirred for 1 h. Theaequous layer was extracted three times with 100 ml chloroform. Thecombined organic layers were evaporated in vacuo. The raw product waspurified by column chromatography (450 g silicagel, eluent hexane/ethylacetate 15:1, vol. ratio). 3.2 g (26 %)N,N-Dibutyl-4-amino-2-hydroxy-benzaldehyde was obtained as an orangeoily compound.

[0074] b) Preparation of the ligand 2a

[0075] To a solution of 1 g (0.004 mol) 4N,N-dibutyl-4-amino-2-hydroxy-benzaldehyde in 2 ml ethanol at 55° C.were added dropwise 0.13 ml (0.00191 mol) of ethylene diamine. Theresulting clear solution was kept under stirring for 4 h between 60-65°C. The solution was cooled and the precipitate formed was filtered anddried to give 540 mg (54%) of a slightly brownish solid.

[0076]¹³C NMR (CDCl₃): δ=14.0 (aliph. CH₃), 20.2, 29.5, 50.8, 58.2(aliph. CH₂), 98.2, 103.1, 132.9 (tert. Aryl-C), 108.2, 151.9, 165.7(quart Aryl-C), 164.3 (C═N).

[0077] Calc. C 73.52 H 9.65 N 10.72

[0078] Found C 73.14 H 9.34 N 10.55

Ligand 2b

[0079] Preparation of the corresponding aldehyde:

[0080] A solution of 13 g (0.04255 mol) of N,N-heptyl-3-amino-phenol,prepared after the procedure described in EP 0356173, in 30 mlchloroform was treated with 6.7 g (0.04255 mol) of phosphorusoxychloride and 12.4 g (0.169 mol) of N,N-dimethyl formamide andworked-up as described for compound 2a. Purification was accomplished bycolumn chromatography a mixture of chlorobenzene/ethyl acetate/ethanol(90:5:5, vol. ratio). 1.78 g (13%) ofN,N-heptyl-4-amino-2-hydroxy-benzaldehyde was obtained as a green oilycompound.

[0081] A solution of 0.8 g (0.0024 mol)N,N-heptyl-4-amino-2-hydroxy-benzaldehyde in 1 ml ethanol was treatedand worked-up as described for compound 2a. 720 mg (91%) of the ligandwas obtained as a brown oil which slowly crystallized when stored at 5°C. for three days.

[0082]¹³C NMR (CDCl₃): δ=14.1 aliph. CH₃), 22.6, 27.1, 27.5, 29.2, 31.9,51.0, 57.7 (aliph. CH₂), 98.3, 103.2, 133.0 (tert. Aryl-C), 108.2,152.1, 166.5 (quart Aryl-C), 164.2 (C═N).

[0083] Calc. C 76.47 H 10.79 N 8.11

[0084] Found C 76.18 H 10.60 N 7.95

Ligand 2c

[0085] To a stirred solution of 2 g (0.0121 mol) of5-dimethylamino-2-hydroxy-benzaldehyde [prepared after Bull. Chem. Soc.Jpn. 51 (1978) 2433] in 6 ml ethanol at 50° C. was added dropwise 0.35 g(0.0058 mol) of ethylene diamine. An orange suspension was formed whichwas stirred at 60° C. for 4 h. The suspension was cooled to roomtemperature, filtered and dried in vacuo at 30° C. The pure ligand wasobtained as a yellow solid (1.77 g, 87%).

[0086]¹³C NMR (CDCl₃): δ=45.0 (aliph. NCH₃), 60.0 (aliph. CH₂), 116.2,117.2, 119.6 (tert. Aryl-C), 118.4,144.2,153.3 (quart Aryl-C), 166.8(C═N).

[0087] Calc. C 67.77 H 7.39 N 15.81

[0088] Found C 67.56 H 7.35 N 15.25

Ligand 2d

[0089] To a solution of 2.5 g (0.015 mol)N,N-dimethyl-4-amino-2-hydroxy-benzaldehyde in 7 ml ethanol was addedwithin 2 minutes a solution of 0.82 g (0.00721 mol) of diamino maleicacid dinitrile in 14 ml methanol. The reaction mixture was heated for 5h at 65° C. A brown suspension was obtained which was cooled, filteredand dried to give a brown solid (2.03 g, 70%).

[0090]¹³C NMR (CDCl₃): δ=40.0 (aliph. NCH₃), 110.4, 115.1 (aliph. quart.C), 98.2, 105.8, 133.0 (tert. Aryl-C), 110.4, 115.1, 161.2 (quartAryl-C), 156.2 (C═N).

Ligand 2e

[0091] A solution of 5.0 g (0.0259 mol)4-diethylamino-2-hydroxy-benzaldehyde in 12 ml ethanol was treated with1.66 g (0.0123 mol) of bis-(3-aminopropyl)amine and worked-up asdescribed for ligand 2a. The raw product was dried in high vacuo to give5.7 g (98%) of a red oil.

[0092]¹³C NMR (CDCl₃): δ=12.8 (aliph. CH₃), 31.1, 44.5, 47.2, 53.6(aliph. CH₂), 98.7, 103.1, 133.2 (tert. Aryl-C), 108.2, 152.2, 169.0(quart Aryl-C), 162.5 (C═N).

[0093] Calc. C 68.77 H 9.00 N 14.32.

[0094] Found C 67.09 H 8.66 N 13.38 (Substance contains 1.51% water)

Ligand 2f

[0095] A solution of 0.81 g (0.00517 mol)4-chloro-2-hydroxy-benzaldehyde prepared after Beilstein (E IV, vol. 8,223) in 2.5 ml ethanol was treated with 0.29 g (0.00246 mol)trans-1,2-diaminohexane and worked-up as described for ligand 2a. Theligand was obtained as a yellow oil (0.96 g, 100%) which upon standingslowly crystallized.

[0096]¹³NMR (CDCl₃): δ=24.1, 32.9 (CH₂), 54.6, 72.4 (CH), 117.0, 138.1,162.0 (quart Aryl-C), 117.2, 118.9 (tert. Aryl-C), 164.0(C═N).

[0097] Calc. C 61.39 H 5.15 N 7.16 Cl 18.12

[0098] Found C 61.50 H 5.34 N 7.70 Cl 17.26

Ligand 2g

[0099] To a stirred solution of 2 g (0.013 mol)2-hydroxy-4-methoxy-benzaldehyde in 10 ml ethanol at room temperaturewere added at once 579 mg (0.0065 mol) 1,2-diethylamino-2-methylpropane.The solution was heated at 60° C. for 3 h and cooled to roomtemperature.

[0100] The clear solution was evaporated and dried in high vacuo to givethe ligand as a red-brown oil (2.58 g, 100%).

[0101]¹³C NMR (CDCl₃): δ=25.3((CH₃)₂C—), 55.3 (OCH₃), 59.2 (aliph,quart. C), 69.2 (NCH₂), 101.2, 101.4 (tert. Aryl-C), 106.3, 106.4 (tert.Aryl-C), 112.2, 112.3 (quart Aryl-C), 132.9, 133.1 (tert. Aryl-C),160.3, 165.6 (C═N), 163.7, 163.9 (quart. Aryl-C), 165.0, 166.7 (quart.Aryl-C).

[0102] Calc. C 67.39 H 6.79 N 7.86

[0103] Found C 67.51 H 6.91 N 7.69

Ligand 2h

[0104] 2 g (0.0103 mol) 4-diethylamino-2-hydroxy-benzaldehyde and 456 mg(0.00517 mol) 1,2-diethylamino-2-methylpropane were treated andworked-up as described for ligand 2g. The ligand was obtained as ared-brown solid (1.9 g, 84%).

[0105]¹³C NMR (CDCl₃): δ=12.7 (CH₃CH₂N), 25.4 ((CH₃)₂C—), 44.4(NCH₂CH₃), 58.4 (quart. C), 68.6 (NCH₂), 98.1, 98.6 (tert. Aryl-C),103.0, 103.1 (tert. Aryl-C), 108.3, 108.4 (quart Aryl-C), 133.1, 133.4(tert. Aryl-C), 151.6, 151.9 (quart. Aryl-C), 158.9, 164.5 (C═N), 166.0,168.4 (quart. Aryl-C).

[0106] Calc. C 71.91 H 8.74 N 12.72

[0107] Found C 70.88 H 8.65 N 12.35

Ligand 2i

[0108] 1.21 g (0.006 mol) 4-diethylamino-2-hydroxy-benzaldehyde wasdissolved under stirring in 2 ml ethanol at 50° C. At this temperature,a solution of 2,3-diamino-2,3-dimethyl-butane (prepared after BeilsteinE IV, vol. 4, 1354) in 2 ml ethanol was added within 30 minutes. Thereaction mixture was heated to 70 C. for 3 h and stirred at roomtemperature for another 8 h.

[0109] The resulting suspension was filtered and the precipitate waswashed with cold ethanol and dried in high vacuo to give a brown solid(890 mg, 66%).

[0110]¹³C NMR (CDCl₃): δ=12.8, 23.0 (CH₃), 44.5 (CH₂), 63.3 (quart.alipht. C), 98.6,103.0, 133.5 (tert. Aryl-C), 108.2, 152.1, 169.1(quart. Aryl-C), 158.9 (C═N).

[0111] Calc. C72.07 H 9.07 N 12.01

[0112] Found C71.78 H 9.03 N 11.88

Ligand 2j

[0113] To a solution of 974 mg (0.0045 mol)2,3,6,7-tetrahydro-8-hydroxy-1H,5H-benzo[ij]quinolizine-9-carboxaldehydein 30 ml methanol was added a solution of 148 mg (0.0025 mol) ethylenediamine. The reaction mixture was heated under reflux for 1 h. Theformed precipitate was filtered and crystallized in 100 ml of methanolto yield 590 mg (29%) of yellow crystals.

[0114]¹³C NMR (CDCl₃): δ=20.4, 21.3, 22.2, 27.2, 49.8, 50.1, 58.2 (CH₂),106.8, 107,9, 112,2, 129.0, 146.4, 164.3 (C═N).

[0115] Calc. C 73.33 H 7.47 N 12.22

[0116] Found C 73.37 H 7.54 N 12.22

Ligand 2k

[0117] A solution of 1.95 g (0.00714 mol)8-hydroxy-1,1,7,7-tetramethyljulolidine-9-carboxaldehyde in 60 mlmethanol was reacted with 236 mg (0.0393 mmol) ethylene diamine asdescribed for ligand 2j. The precipitate was filtered and washed withmethanol to give 1.52 g (75%).

[0118]¹³C NMR (CDCl₃): δ=28.5 (prim. C), 31.2 (prim. C), 31.7, 32.2,36.6, 40.1, 47.0, 47.4, 58.9, 108.7, 114.8, 121.6, 127.5), 145.7, 161.2,165.4 (C═N).

Ligand 2I

[0119] A solution of 5.0 g (0.0355 mol) 2,4-dihydroxy-benzaldehyde in 17ml ethanol was treated with 1.97 g (0.0169 mol) oftrans-1,2-diaminocylohexane and heated at 65° C. for 5 h. A yellowsuspension was formed which was cooled to 2° C. The precipitate wasfiltered, washed with ethanol and dried to give 5.9 g (99%) of a yellowsolid.

[0120]¹³C NMR (DMSO-d₆): δ=24.9, 33.6 (CH₂), 71.3 (CH), 103.3, 107.8,134.1 (tert. Aryl-C), 112.0, 162.6 (quart. Aryl-C), 164.9 (C═N)

Ligand 2m

[0121] A solution of 5 g (0.025 mol)4-diethylamino-2-hydroxy-benzaldehyde in 12 ml ethanol was treated with0.92 g (0.0123 mol) of 1,2-diaminopropane and heated at 65° C. for 5 h.The solution was cooled and stirred for 8 h. The solution wasconcentrated to give 4.68 g (90%) of a brown solid.

[0122]¹³C NMR (CDCl₃): δ=12.7, 20.3 (CH₃), 44.5, 63.8 (CH₂), 98.2,103.1, 133.1 (tert. Aryl-C), 108.3, 151.5, 165.5 (quart. Aryl-C), 162.5(C═N)

[0123] The following ligands are known compounds.

[0124] These ligands were prepared according to known literatureprocedures:

[0125] All described ligands were transformed into its manganesecomplexes. The syntheses of these complexes were performed according tothe literature as described by E. N. Jacobsen et al. J. Org. Chem., 59(1994) 1939 or in Patent GB-A-2,296,015. As an example for the standardprocedure, the synthesis of the manganese complex 1b is described: To astirred solution of 667 mg of ligand 3f dissolved in 10 ml of ethanolwas added 465 mg manganese-II-acetate-tetrahydrate. The reactionsolution was heated at 65-70° C. for 4 h. Afterwards, the solution wasevaporated and the residue was dissolved in 40 ml of water. The solutionwere treated with 3.7 g of sodium chloride. The resulting precipitatewas filtered and dried in vacuo. The manganese complex was obtained asred-brown powder (820 mg, 86%).

EXAMPLE 1

[0126] Each of the test compounds is then evaluated to determine itsactivity as a dye transfer inhibitor according to the following method.

[0127] 7.5 g of white cotton are washed in 80 ml of wash liquor. Thewash liquor contains 8.6 mmol/l H₂O₂, a solution of a test dyestuff and7.5 g/l of the standard detergent ECE phosphate-free (456 IEC) EMPA,Switzerland: 9.74% Sodium linear alkylbenzenesulfonate (Marion A375);5.19% Ethoxylated C₁₂-C₁₈ fatty alcohol (7 moles EO); 3.64% Sodium soap;6.49% Silicon foam inhibitor; 32.47% Sodium aluminium silicate Zeolite4A; 11.82% Sodium carbonate; 5.19% Sodium salt of acrylic acid/maleicacid copolymer (Sokolan CP 5) 3.38% Sodium silicate (SiO₂:Na₂O = 3.3:1);1.30% Carboxymethylcellulose 0.26% EDTA; 7.40% Sodium sulfate; 12.21%Water; 0.65% Proteolytic enzyme prills; 0.26% Fluorescent whiteningagent; 20.0% Sodium percarbonate; and 3.0% TAED.

[0128] The washing is conducted in beakers in a LINITEST apparatus at40° C. over 30 minutes. The test dye transfer inhibitor is added at alevel of 50 μmol/l. The commercially available test dye used is eitherCuprophenyl Brown 2GL (Dye 1) used at a level of 10 mg/l of the 250%formulation, or Reactive Blue 238 (Dye 2) used at a level of 6 mg/l ofthe 100% formulation. The reflection spectra of the respective testsamples are measured with a SPECTRAFLASH 2000 instrument and aretransformed into brightness values according to the CIE standardprocedure.

[0129] The percentage DTI (dye transfer inhibition) effectivity (a) isthen calculated in accordance with the following equation:

a={[Y(E)−Y(A)]/[Y(W)−Y(A)]}×100

[0130] in which Y(W), Y(A) and Y(E), respectively, are theCIE-brightness values of the white material before treatment, of thefabric as obtained when washed without a dye transfer inhibitor and ofthe fabric as obtained when washed with a dye transfer inhibitor. A zeropercent value for the a-value denotes a completely ineffective dyetransfer inhibitor, that is a compound, the addition of which to a washliquor allows full dye transfer on to the white material. By contrast, a100 percent value for a denotes a perfect dye transfer inhibitor, thatis a compound, the addition of which to a wash liquor allows no dyetransfer on to the white material.

[0131] The results obtained are set out in the following Table 1. TABLE1 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye 2 inhibitor1(A) 90 98 inhibitor 1(B) 82 87 inhibitor 1(C) 80 85 inhibitor 1(D) 8486 Manganese complexes of ligand 2a 71 2b 78 2c 70 2d 73 2e 68 2f 84 2g80 2h 87 2i 69 2j 90 2k 77 2l 85 2m 85

[0132] TABLE 1b DTI-effiency of manganese complexes derived from knownligands Test dye transfer inhibitor DTI effectivity (a) 3a 92 3b 74 3c76 3d 61 3e 78 3f (Ligand for Mn complex 1b) cf. TABLE 1 3g (Ligand forMn complex 1c) ″ 3h (Ligand for Mn complex 1a) ″ 3l (Ligand for Mncomplex 1d) ″ 3j 97

[0133] The results in Table 1 clearly demonstrate that claimed manganesecomplexes exhibit excellent performance as dye transfer inhibitors.

EXAMPLE 2

[0134] The procedure in Example 1 is repeated with the exceptions thatonly inhibitors 1(A) and 1(B) are used and that the amounts used ofthese inhibitors are varied over a wide range.

[0135] The results obtained are set out in the following Table 2. TABLE2 Test dye transfer DTI effectivity (a) inhibitor Concentration μmol/lDye 1 Dye 2 inhibitor 1(A)  5 59 64 10 69 85 20 83 95 30 90 103  50 9098 70 98 105  inhibitor 1(B)  5 50 43 10 61 76 20 76 78 30 77 78 50 8287 70 82 88

[0136] The results in Table 2 show that manganese complexes of formula(1) exhibit excellent performance as dye transfer inhibitors even atvery low levels of addition.

EXAMPLE 3

[0137] The procedure in Example 1 is repeated with the exceptions thatonly inhibitors 1(A) and 1(B) are used and that their effectiveness incontrolling transfer of a wide range of dyes, at various levels of dyeaddition, is examined. The results obtained are set out in the followingTable 3. TABLE 3 DTI effectivity (a) Test dye Concentration μmol/linhibitor 1(A) inhibitor 1(B) Cuprophenyl Brown 2GL 250% 10 90 82Reactive Blue 238 100% 6 98 87 Reactive Black 5 133% 12 80 65 DirectBlack 22 400% 6 76 73 Reactive Blue 19 Special 100% 20 97 88 Acid Blue113 180% 6 96 90 Disperse Violet 1 100% 6 90 72

[0138] The results in Table 3 show that manganese complexes of formula(1) exhibit excellent performance as dye transfer inhibitors againstmigration of a a wide range of dyes, at various levels of dye addition.

EXAMPLE 4

[0139] The procedure in Example 1 is repeated for a washing temperatureof 20° C.

[0140] The results obtained are set out in the following Table 4. TABLE4 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye 2 inhibitor1(A) 82 86 inhibitor 1(B) 79 73 inhibitor 1(C) 70 86 inhibitor 1(D) 8080

[0141] The results in Table 4 show that manganese complexes of formula(1) exhibit excellent performance as dye transfer inhibitors even atwashing temperatures as low as 20° C.

EXAMPLE 5

[0142] The procedure in Example 1 is repeated with the exceptions thatonly inhibitors 1(A) and 1(B) are used and that the detergentcomposition used is modified by the addition of 4% by weight of TAED, asbleach activator.

[0143] The results obtained are set out in the following Table 5. TABLE5 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye 2 inhibitor1(A) 99 100 inhibitor 1(B) 96  97

[0144] The results in Table 5 show that manganese complexes of formula(1) exhibit excellent performance as dye transfer inhibitors and thattheir effectiveness is not impaired by their co-use with activatedbleach systems.

[0145] Moreover, the compatibility between manganese complexes offormula (1) and activated bleach systems has recriprocal benefits. Inparticular, under the conditions described in Example 1, thebleach-promoting action of TAED is maintained, even in the presence of20 μM of a manganese complex of formula (1). Thus, the brightnessincrease (ΔY) obtained with tea-stained cotton test material is 24 whenno dye transfer inhibitor is present (control test); 23 using inhibitor1(A); and 24 using inhibitor 1(B).

EXAMPLE 6

[0146] The procedure in Example 1 is repeated with the exceptions thatonly inhibitors 1(A) and 1(B) are used and that the detergentcomposition used is modified by the addition of 100 μM of DEQUEST 2041[ethylenediamine-tetra-(methylenephosphonic acid)], as sequesteringagent.

[0147] The results obtained are set out in the following Table 6. TABLE6 DTI effectivity (a) Test dye transfer inhibitor Dye 1 Dye 2 inhibitor1(A) 20 μmol/l 50 μmol/l 20 μmol/l 50 μmol/l without DEQUEST 83 90 95 98with DEQUEST 89 93 95 98 inhibitor 1(B) 20 μmol/l 50 μmol/l 20 μmol/l 50μmol/l without DEQUEST 76 82 78 87 with DEQUEST 82 87 79 83

[0148] The results in Table 6 show that manganese complexes of formula(1) exhibit excellent performance as dye transfer inhibitors and thattheir effectiveness is not impaired by their co-use with a sequesteringagent. Sequestering agents are usually present in detergent formulationsand their presence can often lead to the observation of higher a-values.This is because heavy metal ions are masked, and therefore the reservoirof peroxidic oxygen is not depleted by useless degradation processes.

EXAMPLE 7

[0149] The procedure in Example 1 is repeated with the exceptions thatonly inhibitors 1(A) and 1(B) are used and that the amounts used of H₂O₂in the detergent are varied.

[0150] The results obtained are set out in the following Table 7. DTIeffectivity (a) inhibitor 1(A) inhibitor 1(B) H₂O₂ Concentration μmol/lDye 1 Dye 2 Dye 1 Dye 2 2.1 84 85 65 60 4.3 86 88 83 79 8.6 89 89 85 82

[0151] The results in Table 7 show that, even when the conventionalamount of H₂O₂ present in the detergent formulation is reduced by afactor of 4, the effectiveness of manganese complexes of formula (1) asdye transfer inhibitors is retained.

EXAMPLE 8

[0152] The procedure in Example 1 is repeated with the exceptions thatonly inhibitors 1(A) and 1(B) are used and that a series of dyed cottonfabrics is used which are known to very sensitive to aggressivebleaching systems. For the purpose of comparison, an analogous testusing TAED instead of inhibitor 1(A) or 1(B) is conducted. The washingtreatment is carried out five times with each respective detergentcomposition and, after completion of the fifth respective wash, thepercentage loss of dye is determined.

[0153] The results are set out in the following Table 8. TABLE 8 %Dyestuff Loss Test Dye inhibitor 1(A) inhibitor 1(B) TAED Reactive Brown017 16 17 15 Vat Brown 001  0  4  2 Reactive Red 123 16 10 13 DirectBlue 085 18 14 14

[0154] The results in Table 8 show that the dyestuff loss observed whenusing a detergent containing a manganese complex of formula (1) as dyetransfer inhibitor, is of the same order as that experienced when adetergent containing a TAED-activated bleach system is used. The latterdetergent composition represents the state of the art for oxygenbleaches, and its dye damage/usefulness balance is accepted in theindustry.

[0155] Using the same test conditions, after completion of the fifthrespective wash, the percentage relative reduction of DP (average degreeof polymerisation) is determined, in order to assess the damage to thefiber.

[0156] The results are set out in the following Table 9. TABLE 9 %Relative DP-Reduction Test Dye inhibitor 1(A) inhibitor 1(B) TAEDReactive Brown 017  4 12 5 Vat Brown 001 18 20 19  Reactive Red 123 2619 7 Direct Blue 085  0  1 2

[0157] The results in Table 9 show that the fiber damage on dyed cottonmaterial observed when using a detergent containing a manganese complexof formula (1) as dye transfer inhibitor, is of the same order as thatexperienced when a detergent containing a TAED-activated bleach systemis used.

1. A process for inhibiting the re-absorption of migrating dyes in thewash liquor, comprising introducing into a wash liquor containing aperoxide-containing detergent, from 0.5 to 150 mg, per liter of washliquor, of one or more compounds having the formula:

in which n is 1, 2 or 3; A is an anion; R₁ is hydrogen or C₁-C₄-alkyl, Yis linear or branched alkylene of the formula —[C(R₁)₂]_(m) in which mis an integer ranging from 1 to 8 and each R₁ independently from theothers has its previous significance; —CX═CX— in which X is cyano,linear or branched C₁-C₈-alkyl or di(linear or branchedC₁-C₈-alkyl-amino; —(CH₂)_(q)—NR₁—(CH₂)_(q)— in which R₁ has itsprevious significance and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene orphenylene residue having the formula:

 in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M is hydrogen,an alkali metal atom, ammonium or a cation formed from an amine, R andR′ are each independently from the other cyano; halogen; hydroxy; OR, orCOOR₁ in which R₁ has its previous significance; nitro; linear orbranched partially or completely fluorinated C₁-C₈-alkyl; NR₃R₄ in whichR₃ and R₄ are the same or different and each is hydrogen or linear orbranched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄ have theirprevious significance or linear or branched C₁-C₈-alkylene-R₂ in whichR₂ is OR₁, COOR₁ or NR₃R₄, R₅ and R₆ are each independently from theother hydrogen; linear or branched C₁-C₄-alkyl; unsubstituted aryl oraryl which is substituted by cyano, halogen, OR₁ or COOR₁, nitro, linearor branched C₁-C₈-alkyl, NR₃R₄ in which R₃ and R₄ are the same ordifferent and each is hydrogen or linear or branched C₁-C₁₂-alkyl;—N⊕R₁R₃R₄ in which R₁, R₃ and R₄ have their previous significance orlinear or branched C₁-C₈-alkylene-R₂ in which R₂ is OR₁, COOR₁ or NR₃R₄,with the proviso that each n is 1, if R and R′ are both C₁-C₄-alkyl. 2.A process according to claim 1 in which from 1.5 to 75 mg, per liter ofwash liquor, of one or more compounds having the formula (1) or (2) isintroduced into the wash liquor.
 3. A process according to claim 2 inwhich from 7.5 to 40 mg, per liter of wash liquor, of one or morecompounds having the formula (1) or (2) is introduced into the washliquor.
 4. A process according to claim 1 in which the anion A ishalide, perchlorate, sulphate, nitrate, hydroxide, BF₄ ⁻, PF₆ ⁻ or acarboxylate.
 5. A process according to claim 4 in which the halide anionA is chloride.
 6. A process according to claim 4 in which thecarboxylate anion A is acetate, triflate or tosylate.
 7. A processaccording to claim 1 in which Y is —[C(R₈)₂]₂ wherein R₈ is hydrogen ormethyl, —CX═CX— in which X is cyano, —(CH₂)_(q)—NR₈—(CH₂)_(q)— in whichR₈ has its previous significance and q is 1, 2, 3 or 4; or a1,2-cyclohexylene or phenylene residue having the formula:


8. A process according to claim 1 in which R and R′ are dimethylamino,diethylamino, hydroxy, methoxy, ethoxy, chloro or nitro.
 9. A processaccording to claim 1 in which when n is 1, the group R or R′ is in the4-position of the respective benzene ring, with the exceptions that whenR or R′ is nitro or CO₂R₂, the group R or R′ is in the 5-position of therespective benzene ring.
 10. A process according to claim 1 in whichwhen n is 2, the groups R or R′ are in the 4,6-positions of therespective benzene ring, with the exceptions that when R or R′ is nitroor CO₂R₂ the groups R or R′ are in the 3,5-positions of the respectivebenzene ring.
 11. A process according to claim 1 in which R or R′ isdi-(C₁-C₁₂alkyl)amino, preferably di-(C₁-C₈alkyl)amino.
 12. A processaccording to claim 11 in which the alkyl moiety in the groupdi-(C₁-C₁₂alkyl)amino contains from 1 to 4 carbon atoms.
 13. A processaccording to claim 12 in which the alkyl moiety in the groupdi-(C₁-C₁₂alkyl)amino contains 1 or 2 carbon atoms.
 14. A processaccording to claim 1 in which the compound of formula (1) is one or moreof the compounds of formulae:


15. A detergent composition comprising: i) 5-90% of A) an anionicsurfactant and/or B) a nonionic surfactant; ii) 5-70% of C) a builder;iii) 0.1-30% of D) a peroxide; and iv) 0.005-2% of E) a compound offormula (1) or (2) as defined in claim 1 , each by weight, based on thetotal weight of the detergent.
 16. A composition according to claim 15comprising: i) 5-70% of A) an anionic surfactant and/or B) a nonionicsurfactant; ii) 5-50% of C) a builder; iii) 1-12% of D) a peroxide; andiv) 0.02-1% of E) a compound of formula (1) or (2) as defined in claim 1, each by weight, based on the total weight of the detergent.
 17. Acomposition according to claim 16 comprising: i) 5-70% of A) an anionicsurfactant and/or B) a nonionic surfactant; ii) 5-40% of C) a builder;iii) 1-12% of D) a peroxide; and iv) 0.1-0.5% of E) a compound offormula (1) or (2) as defined in claim 1 , each by weight, based on thetotal weight of the detergent.
 18. A composition according to claim 15comprising a combination of two or more of the compounds of formula (1)or (2) as defined in claim 1 .
 19. A composition according to claim 15comprising 0.5-5% by weight of a polymer useful in preventing thetransfer of labile dyes between fabrics during a washing cycle.
 20. Acomposition according to claim 19 comprising 0.2-1.7% of the polymer.21. A composition according to claim 19 in which the polymer is apolyvinylpyrrolidone optionally containing an anionic or cationicsubstituent.
 22. A composition according to claim 15 in which thedetergent is in powder or granulate form.
 23. A composition according toclaim 15 in which the detergent is in liquid form and contains 0-5%water.
 24. A composition according to claim 23 in which the detergent isin liquid form and contains 0-1% water.
 25. A composition according toclaim 15 , containing additionally TAGU or TAED:
 26. A process for theproduction of a detergent as claimed in claim 22 in which the componentsof the detergent are mixed in dry form.
 27. A process for the productionof a detergent as claimed in claim 22 in which a base powder is producedby spray-drying an aqueous slurry which contains all the componentsdefined in claim 22 , apart from the components D) and E); and thenadding the components D) and E) by dry-blending them into the basepowder.
 28. A process for the production of a detergent as claimed inclaim 22 in which the component E) is added to the slurry containingcomponents A), B) and C), which slurry is then spray-dried beforecomponent D) is dry-blended into the mixture.
 29. A process for theproduction of a detergent as claimed in claim 22 in which component B)is not present, or is only partly present in a slurry containingcomponents A) and C); the component E) is incorporated into componentB), which is then added to the spray-dried base powder;and finallycomponent D) is dry-blended into the mixture.
 30. Manganese complexes offormula (3)

in which n is 1, 2 or 3; A is an anion; R and R′ are each independentlyfrom the other cyano; halogen; hydroxy; OR₁ or COOR₁ in which R₁ has itsprevious significance; nitro; linear or branched partially or completelyfluorinated C₁-C₈-alkyl; NR₃R₄ in which R₃ and R₄ are the same ordifferent and each is hydrogen or linear or branched C₁-C₁₂-alkyl;—N⊕R₁R₃R₄ in which R₁, R₃ and R₄ have their previous significance orlinear or branched C₁-C₈-alkylene-R₂ in which R₂ is OR₁, COOR₁ or NR₃R₄,R₁ is hydrogen or C₁-C₄-alkyl, Y₁ is —CX═CX— in which X is cyano,—(CH₂)_(q)—NR₁—(CH₂)_(q)— in which R₁ has its previous significance andq is 1, 2, 3 or 4; linear or branched alkylene of the formula—[C(R₁)₂]_(m) in which m is an integer ranging from 1 to 8 and each R₁independently from the other has its previous significance, with theproviso that at least one R₁ is C₁-C₄-alkyl; or a 1,2-cyclohexylene orphenylene residue having the formula:

 in which R₇ is hydrogen, CH₂OH or CH₂NH₂or SO₃M, where M is hydrogen,an alkali metal atom, ammonium or a cation formed from an amine, withthe proviso that each n is 1 if R and R′ are both C₁-C₄-alkyl and Y₁ isan unsubstituted 1,2-cyclohexylene residue, Y is linear or branchedalkylene of the formula —[C(R₁)₂]_(m) in which m is an integer rangingfrom 1 to 8 and each R₁ independently from the other has its previoussignificance; —CX═CX— in which X is cyano, linear or branchedC₁-C₈-alkyl or di(linear or branched C₁-C₈-alkyl)-amino;—(CH₂)_(q)—NR₁—(CH₂)_(q)— in which R₁ has its previous significance andq is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue havingthe formula:

 in which R₇ is hydrogen, CH₂OH or CH₂NH₂or SO₃M, where M is hydrogen,an alkali metal atom, ammonium or a cation formed from an amine, R₅ andR₆ are each independently from the other hydrogen; linear or branchedC₁-C₄-alkyl; unsubstituted aryl or aryl which is substituted by cyano,halogen, OR₁ or COOR₁, nitro, linear or branched C₁-C₈-alkyl, NR₃R₄ inwhich R₃ and R₄ are the same or different and each is hydrogen or linearor branched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄ have theirprevious significance or linear or branched C₁-C₈-alkylene-R₂ in whichR₂ is OR₁, COOR₁ or NR₃R₄.
 31. Compounds of the formula (4)

in which n is 1, 2 or 3; R and R′ are each independently from the othercyano; halogen; hydroxy; OR₁ or COOR₁ in which R₁ has its previoussignificance; nitro; linear or branched partially or completelyfluorinated C₁-C₈-alkyl; NR₃R₄ in which R₃ and R₄ are the same ordifferent and each is hydrogen or linear or branched C₁-C₁₂-alkyl;—N⊕R₁R₃R₄ in which R₁, R₃ and R₄ have their previous significance orlinear or branched C₁-C₈-alkylene-R₂ in which R₂ is OR₁, COOR₁ or NR₃R₄,R₁ is hydrogen or C₁-C₄-alkyl, Y₁ is —CX═CX— in which X is cyano,—(CH₂)_(q)—NR₁—(CH₂)_(q)— in which R₁ has its previous significance andq is 1, 2, 3 or 4; linear or branched alkylene of the formula—[C(R₁)₂]_(m) in which m is an integer ranging from 1 to 8 and each R₁independently from the other has its previous significance, with theproviso that at least one R₁ is C₁-C₄-alkyl; or a 1,2-cyclohexylene orphenylene residue having the formula:

 in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M is hydrogen,an alkali metal atom, ammonium or a cation formed from an amine, withthe proviso that each n is 1 if R and R′ are both C₁-C₄-alkyl and Y₁ isan unsubstituted 1,2-cyclohexylene residue, p1 Y is linear or branchedalkylene of the formula —[C(R₁)₂]_(m) in which m is an integer rangingfrom 1 to 8 and each R₁ independently from the other has its previoussignificance; —CX═CX— in which X is cyano, linear or branchedC₁-C₈-alkyl or di(linear or branched C₁-C₈-alkyl)-amino;—(CH₂)_(q)—NR₁—(CH₂)_(q)— in which R₁ has its previous significance andq is 1, 2, 3 or 4; or a 1,2-cyclohexylene or phenylene residue havingthe formula:

 in which R₇ is hydrogen, CH₂OH or CH₂NH₂ or SO₃M, where M is hydrogen,an alkali metal atom, ammonium or a cation formed from an amine, R₅ andR₆ are each independently from the other hydrogen; linear or branchedC₁-C₄-alkyl; unsubstituted aryl or aryl which is substituted by cyano,halogen, OR₁ or COOR₁, nitro, linear or branched C₁-C₈-alkyl, NR₃R₄ inwhich R₃ and R₄ are the same or different and each is hydrogen or linearor branched C₁-C₁₂-alkyl; —N⊕R₁R₃R₄ in which R₁, R₃ and R₄ have theirprevious significance or linear or branched C₁-C₈-alkylene-R₂ in whichR₂ is OR₁, COOR₁ or NR₃R₄.
 32. Compounds of the formula